Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

• the present disclosure provides a condensation polyamide composition suitable for blow molding, methods for making the compositions and parts blow-molded from the composition.
• the present invention provides a blow-moldable composition.
• the blow-moldable composition includes a polyamide composition, a reacted composition that is a reaction product of the polyamide composition, or a combination thereof.
• the polyamide composition includes >30 wt% to ⁇ 90 wt% polyamide-6,6, from >0 wt% to ⁇ 10 wt% of a reinforcing fiber, and from >0 to ⁇ 1 wt% of nylon-6.
• the blow-moldable composition is extrudable downwardly at a temperature of 260 °C to 310 °C into a parison having a wall thickness of Wi at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and a wall thickness of the parison throughout differs from Wi by less than 30% of Wi for at least 30 seconds after the length of 1 meter is reached.
• the present invention provides a blow-moldable composition.
• the blow-moldable composition includes a polyamide composition, a reacted composition that is a reaction product of the polyamide composition, or a combination thereof.
• the polyamide composition includes >30 wt% to ⁇ 90 wt% polyamide-6,6, and from >0 wt% to ⁇ 10 wt% of a reinforcing fiber.
• the present invention provides a blow-moldable composition.
• the blow-moldable composition includes a polyamide composition, a reacted composition that is a reaction product of the polyamide composition, or a combination thereof.
• the polyamide composition includes >40 wt% to ⁇ 50 wt% polyamide-6,6, from >0 wt% to ⁇ 2 wt% of a reinforcing fiber, PA66/DI that is from >25 wt% to ⁇ 35 wt% of the polyamide composition, and from >10 wt% to ⁇ 50 wt% of a maleic anhydride-grafted polyolefin.
• the maleic anhydride- grafted polyolefin has a grafted maleic anhydride incorporation of >0.05 to ⁇ 1.5 wt% based on total weight of the maleic anhydride-grafted polyolefin.
• the blow-moldable composition is extrudable downwardly at a temperature of 260 °C to 310 °C into a parison having a wall thickness of Wi at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and a wall thickness of the parison throughout differs from Wi by less than 30% of Wi for at least 30 seconds after the length of 1 meter is reached.
• the present invention provides a blow molded article.
• the blow molded article includes a polyamide composition, a reacted composition that is a reaction product of the polyamide composition, or a combination thereof.
• the polyamide composition includes >40 wt% to ⁇ 50 wt% polyamide-6,6, from >0 wt% to ⁇ 2 wt% of a reinforcing fiber, PA66/DI that is from >25 wt% to ⁇ 35 wt% of the polyamide composition, and from >10 wt% to ⁇ 50 wt% of a maleic anhydride-grafted polyolefin.
• the maleic anhydride- grafted polyolefin has a grafted maleic anhydride incorporation of >0.05 to ⁇ 1.5 wt% based on total weight of the maleic anhydride-grafted polyolefin.
• the present invention provides a method of making the blow- moldable composition described herein.
• the method includes combining polyamide-6,6 and maleic anhydride-grafted polyolefin to form the blow-moldable composition.
• the present invention provides a method of making a blow molded article from the blow-moldable composition described herein.
• the method includes blow molding the blow-moldable composition to form the blow molded article.
• the blow-moldable composition of the present invention is free of reinforcing fibers such as glass fibers and is therefore easier to compound and prepare.
• the blow-moldable composition of the present invention can have sufficient melt strength and crystallization behavior to form a stable parison for blow molding applications.
• articles formed from the blow-moldable composition of the present invention can be recycled and/or reused such as to make more of the blow-moldable composition, wherein subsequent articles formed from the recycled article have substantially the same physical properties as the original blow-molded article.
• the blow-moldable composition of the present invention can be used to form articles that can serve as replacements for metal articles, that can have advantageously lower weight than corresponding articles formed from metal or other blow-moldable compositions, and/or that can provide advantageous physical, mechanical, and/or chemical properties at lower cost than articles formed from other blow- moldable compositions such as PAI 2 or PEEK.
• substantially refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.
• substantially free of can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that about 0 wt% to about 5 wt% of the composition is the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.
• polymer refers to a molecule having at least one repeating unit and can include copolymers.
• PA66 refers to a polymer synthesized by polycondensation of hexamethylenediamine (HMD) and adipic acid.
• HMD hexamethylenediamine
• the polymer is also known as Polyamide 66, Nylon 66, nylon 6-6, nylon 6/6 or nylon-6, 6.
• the polyamide-6,6 can have any suitable relative viscosity (RV), such as determined via a formic acid method (e.g., ASTM D789), such as equal to or greater than 35, 40, or 45, or such as equal to or less than 100, 90, or 80, or such as less than or equal to 100 but equal to or greater than 20, 22, 24, 26, 28, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95, or such as 20-80, 25-75, or 30-50, or such as 20-100, 25-90, or 30-80.
• the polyamide composition is substantially free of polyamides other than polyamide-6,6.
• the polyamide composition includes one or more other polyamides other than polyamide-6,6, such as a PA66 copolymer.
• the polyamide composition can be substantially free of reinforcing fibers, such as glass fibers and/or other reinforcing fibers.
• the polyamide composition can be >0 wt% to ⁇ 10 wt% reinforcing fibers, >0 wt% to ⁇ 5 wt%, >0 wt% to ⁇ 2 wt%, >0 wt% to ⁇ 1 wt%, or >0 wt% to ⁇ 0.1 wt% reinforcing fibers, or less than or equal to 10 wt% and greater than or equal to 0 wt%, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, or 9 wt% reinforcing fibers.
• the maleic anhydride-grafted polyolefin can form any suitable proportion of the polyamide composition, such as from >10 wt% to ⁇ 50 wt%, >15 wt% to ⁇ 40 wt%, >25 wt% to ⁇ 35 wt%, or less than or equal to 50 wt% and greater than or equal to 10 wt%, 12, 14, 16, 18, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 38, 40, 42, 44, 46, or 48 wt%.
• the maleic anhydride-grafted polyolefin includes a polyolefin or polyacrylate backbone having pendant maleic anhydride groups grafted thereto.
• the maleic anhydride-grafted polyolefin can have any suitable grafted maleic anhydride incorporation, such as a grafted maleic anhydride incorporation of less than 10 wt%, or of 0.01 to 10 wt%, based on total weight of the maleic anhydride-grafted polyolefin, such as >0.05 to ⁇ 1.5 wt%, >0.1 to ⁇ 1.4 wt%, >0.15 to ⁇ 1.25 wt%, or less than or equal to 1.5 wt% but equal to or greater than 0.05 wt%, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, or 1.5 wt%.
• a suitable grafted maleic anhydride incorporation such as a grafted maleic anhydride incorporation of less than 10 wt%, or of 0.01 to 10 wt%, based on total weight of the maleic an
• the maleic anhydride-grafted polyolefin can have any suitable glass transition temperature (T g ), such as >- 70 °C to ⁇ 0 °C, >-60 °C to ⁇ -20 °C, >-60 °C to ⁇ -30 °C, or less than or equal to 0 °C but greater than or equal to -70 °C, -65, -60, -55, -50, -45, -40, -35, -30, -25, -20, -15, -10, or -5 °C.
• T g glass transition temperature
• the maleic anhydride-grafted polyolefin, or domains thereof can be uniformly distributed in the polyamide composition and/or the reacted product thereof.
• the maleic anhydride-grafted polyolefin can be any suitable maleic anhydride- grafted polyolefin.
• a variety of maleic anhydride-grafted polyolefins are commercially available. These may include, but are not limited to, AMPLIFYTM GR Functional Polymers commercially available from Dow Chemical Co.
• Modification Level (wt%) in Polyolefin means the functionalized level in the polyolefin tested.
• polypropylene with 0.2-0.5 wt% modification level means it is a modified polyolefin having 0.2- 0.5% grafted maleic anhydride content.
• the polyamide composition can further include a PA66 copolymer.
• the PA66 copolymer can form any suitable proportion of the polyamide composition, such as >0 wt% to ⁇ 50 wt%, >10 wt% to ⁇ 50 wt%, >25 wt% to ⁇ 35 wt% of the polyamide composition. Or less than or equal to 50 wt% and greater than or equal to 0 wt%, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 42, 44, 46, or 48 wt%.
• the PA66 copolymer can include any suitable PA66 copolymer, such as nylon 66/6T, nylon 66/DI, nylon 66/D6, nylon 66/DT, nylon 66/610, nylon 66/612.
• the PA66 copolymer can be PA66/DI.
• the polyamide composition can include a chain extender.
• the chain extender can be capable of reacting with the amine and/or acid terminal groups of the PA66, any PA66 copolymer, and/or of the reaction product thereof with the maleic anhydride-grafted polyolefin, thereby connecting two polyamide chains.
• the chain extender can be any suitable chain extender, such as a dialcohol (e.g., ethylene glycol, propanediol, butanediol, hexanediol, or hydroquinone bis(hydroxyethyl)ether), a bis-epoxide (e.g., bisphenol A diglycidyl ether), polymers having epoxide functional groups (e.g., as pendant and/or terminal functional groups), polymers including anhydride functional groups, bis-N-acyl bis-caprolactams (e.g., isophthaloyl bis-caprolactam (IBS), adipoyl bis-caprolactam (ABC), or terephthaloyl bis-caprolactam (TBC)), diphenyl carbonates, bisoxazolines, oxazolinones, diisocyanates, organic phosphites (triphenyl phosphite, caprolactam phosphite
• the chain extender can be a polymer including anhydride functional groups, such as a maleic anhydride-polyolefin copolymer (e.g., an alternating copolymer of maleic anhydride and ethylene).
• the chain extender can be any suitable proportion of the polyamide composition, such as >0.05 to ⁇ 5 wt%, >0.05 to ⁇ 2 wt% of the polyamide composition, >0.1 wt% to ⁇ 1 wt% of the polyamide composition, or less than or equal to 5 wt% but greater than or equal to 0.05 wt%, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, or 4.8 wt%.
• the polyamide composition can further include a modified polyphenylene ether, an impact modifier, a flame retardant, a chain extender, a heat stabilizer (e.g., Zytel® additives (DuPont), Irganox® sterically hindered additives (BASF), and such), a colorant additive, a filler, a conductive fiber, glass fibers, another polyamide other than the polyamide-6,6 and/or PA66 copolymer, or a combination thereof.
• a modified polyphenylene ether e.g., an impact modifier, a flame retardant, a chain extender, a heat stabilizer (e.g., Zytel® additives (DuPont), Irganox® sterically hindered additives (BASF), and such), a colorant additive, a filler, a conductive fiber, glass fibers, another polyamide other than the polyamide-6,6 and/or PA66 copolymer, or a combination thereof.
• Non-limiting examples of optional additives that can be included in the polyamide composition include adhesion promoters, biocides, anti-fogging agents, anti-static agents, anti-oxidants, bonding, blowing and foaming agents, catalysts, dispersants, extenders, smoke suppressants, impact modifiers, initiators, lubricants, nucleants, pigments, colorants and dyes, optical brighteners, plasticizers, processing aids, release agents, silanes, titanates and zirconates, slip agents, anti-blocking agents, stabilizers, stearates, ultraviolet light absorbers, waxes, catalyst deactivators, and combinations thereof.
• the polyamide composition can further include nylon-6, or can be substantially free of nylon-6.
• the blow-moldable composition can further include from >0 to ⁇ 1% by weight of nylon-6, or 0 wt% of nylon-6.
• the blow-moldable composition can exhibit sufficient melt strength to form a parison in a blow molding apparatus, wherein the parison hangs substantially vertically.
• the blow-moldable composition can form a parison that remains substantially stable in an open split mold of a blow molding process for time >1 second and ⁇ 60 seconds.
• the parison can be blow- moldable at ratios of volume to surface area of >2 and ⁇ 20, or >10 and ⁇ 20, or >2 and ⁇ 4, or less than or equal to 20 and greater than or equal to 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19.
• a parison formed from the blow-moldable composition retains sufficient melt strength under blow molding conditions to form a continuous hollow blow-molded molding having a wall thickness of >0.5 mm to ⁇ 20 mm, such as less than or equal to 20 and greater than or equal to 0.5 mm, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, or 18 mm.
• a parison formed from the blow-moldable composition can retain sufficient strength to form a continuous hollow blow-molded molding having aspect ratios from >0.5 to >75, such as less than or equal to 75 and greater than or equal to 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70.
• An aspect ratio is defined as an arithmetic ratio of the overall linear length of a shaped article over its diametric distance.
• the term “stable parison test”, as used herein, describes a test to determine whether a composition is blow-moldable.
• the blow-moldable composition of the present invention can pass the stable parison test.
• the composition passes the stable parison test if the composition is extrudable downwardly into a parison having a wall thickness of Wi at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and the wall thickness throughout differs from Wi by less than 30% of Wi for at least 30 seconds after the hanging length of the parison reaches 1 meter, such as wherein the wall thickness throughout differs from Wi by less than 30% of Wi, 29%, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or by less than 1% of Wi for at least 30 seconds after the hanging length of the parison reaches 1 meter.
• a composition passes the stable parison test if the composition is extrudable downwardly into a parison having a 7 mm wall thickness and a 25 mm outside diameter at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and the wall thickness throughout remains above 6 mm and below 8 mm for at least 30 seconds after the hanging length of the parison reaches 1 meter.
• any suitable temperature can be used for the extrusion of the composition, such as 260 °C to 310 °C, or 275 °C to 290 °C, or less than or equal to 310 °C and greater than or equal to 260 °C, 265, 270, 275, 280, 285, 290, 295, 300, or 305 °C.
• the stable parison test is conducted without pressure or vacuum applied to the inside or outside of the parison.
• the stable parison test is conducted with the parison being pulled down only by the force of gravity and without any other external forces on the parison.
• a blow molded article formed from the blow-moldable composition can be processed and reused to form the blow-moldable composition of the present invention.
• Any suitable proportion of the polyamide composition can be the reused material, such as 0 wt%, or such as 0.01 wt% to 100 wt%, or 30 wt% to 100 wt%, or 30wt% to 80 wt%, or less than or equal to 100 wt% and greater than or equal to 0 wt%, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt%.
• the blow-molded article Before incorporation into the polyamide composition, the blow-molded article can be ground or otherwise formed into particles.
• the particles can have any suitable size, such as 10 mm or less, or equal to or less than 9 mm, 8, 7, 6, 5, 4, 3, 2, or 1 mm.
• Parisons and blow-molded articles formed from the blow-moldable composition that includes the reused material can have substantially the same properties as the original blow-molded article and/or the same properties as a blow-molded article formed from the blow-moldable composition that is substantially free of reused material.
• the blow-moldable composition can include a reacted composition that is a reaction product of the polyamide composition.
• the reacted composition can include a reaction product of the polyamide-6,6 and the maleic anhydride-grafted polyamide, a reaction product of the PA66 copolymer (if present) and the maleic anhydride-grafted polyamide, a reaction product of the polyamide-6,6 and maleic anhydride-polyolefin copolymer (if present), a reaction product of the PA66 copolymer (if present) and maleic anhydride-polyolefin copolymer (if present) or a combination thereof.
• the reacted composition can include a polyamide-polyolefin copolymer formed from at least partial reaction of the polyamide-6,6 and/or PA66 copolymer with the maleic anhydride-grafted polyolefin and/or maleic anhydride-polyolefin copolymer.
• the reacted composition can include the composition including the polyamide-6,6 and/or PA66 copolymer and the maleic anhydride-grafted polyolefin and/or maleic anhydride- polyolefin copolymer wherein any suitable proportion of the polyamide-6,6 and/or PA66 copolymer has reacted with the maleic anhydride-grafted polyolefin and/or maleic anhydridepolyolefin copolymer.
• the reacted composition can include the same components in the same proportions as the composition including the polyamide-6,6 and/or PA66 copolymer and the maleic anhydride-grafted polyolefin and/or maleic anhydride-poly olefin copolymer, with the exception that the polyamide-6,6 and/or PA66 copolymer and the maleic anhydride-grafted polyolefin and/or maleic anhydride-polyolefin copolymer are at least partially reacted.
• the olefin copolymer (structure A) may be any copolymer of ethylene, propylene, or butylene.
• the olefin copolymer may contain a suitable degree of maleation, e.g., maleic anhydride content, for example, between 0.05 to 1.5 % by weight.
• This material can be referred to as “maleic anhydride-grafted polyolefin” (structure C).
• the term “reacted Polyamide-Polyolefin copolymer” or “modified polyamide” (structure E), as used herein is the reacted portion of the polyolefin and the polyamide matrix. This is dependent upon the original maleation content of the polyolefin additive (structure C).
• the term “degree of maleation” or “modification level”, as used interchangeably herein, means the extent of which the olefin copolymer (structure A) has been reacted with maleic anhydride (structure B).
• the polyamide-polyolefin copolymer formed from at least partial reaction of the polyamide-6,6 and/or PA66 copolymer and the maleic anhydride- grafted polyolefin is structure E.
• the maleic anhydride-grafted polyolefin and/or maleic anhydride-polyolefin copolymer, or domains thereof can have a uniform or homogeneous distribution in the polyamide composition or reacted product thereof on a molecular level, such that the molecules of the maleic anhydride-grafted polyolefin and/or maleic anhydride-polyolefin copolymer are homogeneously distributed therein.
• blow molded articles formed from the blow-moldable composition described herein can include a uniform or homogeneous distribution of the maleic anhydride-grafted polyolefin and/or maleic anhydride-polyolefin copolymer, reaction products thereof, or domains of the maleic anhydride-grafted polyolefin and/or maleic anhydride- polyolefin copolymer or reaction products thereof.
• blow molded article that is blow molded from the blow-moldable composition described herein.
• the blow molded article can be any suitable blow molded article that can be blow molded from the blow-moldable composition described herein.
• the blow molded article can have a wall thickness in the range >0.5 mm to ⁇ 20 mm, such as less than or equal to 20 and greater than or equal to 0.5 mm, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, or 18 mm.
• the article can have aspect ratios from >0.5 to >75, such as less than or equal to 75 and greater than or equal to 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70.
• An aspect ratio is defined as an arithmetic ratio of the overall linear length of a shaped article over its diametric distance.
• Various aspects of the present invention provide a method of making the blow- moldable composition described herein.
• the method can include combining the polyamide-6,6, and the maleic anhydride-grafted polyolefin to form the blow-moldable composition.
• a method of forming the article can include making the blow-moldable composition; alternatively, the blow-moldable composition can be pre-formed before the onset of a method of forming the article.
• the method includes combining the polyamide-6,6 and the maleic anhydride-grafted polyolefin (e.g., and allowing the two to at least partially react to form a reaction product thereof) before adding a chain extender thereto.
• the method includes providing to a first compounder extruder zone a feed including the polyamide-6,6 and the maleic anhydride-grafted polyolefin.
• the method can include maintaining the first compounder extruder zone conditions sufficient to obtain a first compounded polyamide melt inside the first compounder extruder zone.
• the method can include introducing a chain extender to the first compounded polyamide melt in a second compounder extruder zone.
• the method can include maintaining the second compounder extruder zone conditions sufficient to obtain a second compounded polyamide melt inside the second compounder extruder zone, wherein the second compounded polyamide melt is the blow- moldable composition described herein.
• the extruder used to make the polyamide composition or the reacted product thereof can be a screw extruder (e.g., a single screw extruder, a vented twin-screw extruder, or an unvented twin-screw extruder).
• a barrel of the screw extruder can include the first compounder extruder zone and the second compounder extruder zone.
• Providing the feed to the first compounder extrusion zone can include providing the feed to a feed inlet of the barrel.
• the chain extender can be introduced to the second compounder extruder zone in the barrel a suitable distance away from the feed inlet.
• the chain extender can be introduced to the second compounder extruder zone at least 1/4 of the length of the barrel from the feed inlet of the barrel.
• the chain extender can be introduced to the second compounder extruder zone at least 1/2 of the length of the barrel from the feed inlet of the barrel.
• the chain extender can be introduced to the second compounder extruder zone at least 3/4 of the length of the barrel from the feed inlet of the barrel.
• the introducing of the chain extender to the first compounded polyamide melt in the second compounder extruder zone can include introducing the chain extender to the first compounded polyamide melt after a certain weight percentage of the maleic anhydride-grafted polyolefin has incorporated into the polyamide composition.
• Incorporation into the polyamide composition can include homogeneous blending of the chain extender with the polyamide composition (e.g., on a molecular level, or of domains of the maleic anhydride- grafted polyolefin or a reaction product thereof), formation of a reaction product of the maleic anhydride-grafted polyolefin (e.g., with the polyamide-6,6 and/or PA66 copolymer), formation of domains of the maleic-anhydride-grafted polyolefin or a reaction product thereof in composition, or a combination thereof.
• the chain extender e.g., on a molecular level, or of domains of the maleic anhydride- grafted polyolefin or a reaction product thereof
• formation of a reaction product of the maleic anhydride-grafted polyolefin e.g., with the polyamide-6,6 and/or PA66 copolymer
• the introducing of the chain extender to the first compounded polyamide melt in the second compounder extruder zone can include introducing the chain extender to the first compounded polyamide melt after at least 50 wt% of the maleic anhydride-grafted polyolefin fed has incorporated into the polyamide composition, or greater than or equal to 50%, 60%, 70%, 80%, 90%, greater than or equal to 95%, or after about 100% of the maleic anhydride-grafted polyolefin has incorporated into the polyamide composition.
• the present invention provides a method of making a blow molded article.
• the method includes making the blow molded article from the blow-moldable composition described herein.
• the method includes blow molding the blow-moldable composition described herein to form the blow molded article.
• Devices for forming parisons in the blow molding of thermoplastics are disclosed in U.S. Patent No. 4,696,636 to Everly et al., and are well known by those of ordinary skill in the art.
• a twin-screw vented extruder having 18-mm diameter co-rotating screw with a 40-56 L/D (i.e., L/D ratio of 40-56) is used for compounding.
• the unit has one main feeder and at least three side feeders.
• a feed rate of at least 1 kg/hr is used.
• the twin-screw co- rotating/turning at least 1000 RPM is sufficient to provide high shear for effective compounding.
• the total compounder throughput is at least 15 kg/hr.
• Polymer, fillers, and additives are continuously fed into the first barrel section of the twin screw using a metering feeder.
• the products are conveyed along the screw and are melted and mixed by kneading elements in the plastification section of the barrel.
• the polymer then travels along to a side port where fillers (if desired), such as but not limited to glass fiber, could be added.
• the polymer then travels on to degassing zones and from there to a pressure build zone where it then exits the die via an at least 3 -mm hole as a lace.
• the cast lace is fed into a water bath to cool and to enable it to be cut into chips via a pelletizer.
• the unit is able to withstand at least 70 bar die pressure.
• a die with a minimum of four holes, each at least 3 mm diameter, is used for pelletizing.
• the compounded pellet having a diameter of 3 mm and a length of 3-5 mm is produced using the above equipment.
• the moisture content of the pelletized material is ⁇ 0.2 wt.%.
• High- AEG polyamide 66 or “High AEG N66” is commercially available from INVISTA.
• High- AEG polyamide 66 is characterized by its RV range of 30-80, for example 35-75 RV, for example, 35-70 RV, and AEG of >65 milliequivalents per kg (meq/kg) and ⁇ 130 meq/kg of the polyamide resin, for example >70 meq/kg and ⁇ 125 meq/kg, >75 meq/kg and ⁇ 125 meq/kg, >80 meq/kg and ⁇ 125 meq/kg, >90 meq/kg and ⁇ 120 meq/kg of the polyamide resin.
• the term “parison” is an extruded rounded mass of molten polymer formed into a tube shape with at least one open end.
• Forming a parison is an intermediate step in blow molding. After the parison is formed, then the parison is clamped into a blow mold and gas is injected into the interior open space of the parison. Similarly, in vacuum molding, gas is drawn into the interior open space of the parison by differential pressure when a vacuum is applied to draw the molten polymer outwardly into contact with the surface of a vacuum mold.
• stable parison describes a parison that can be formed from a composition that passes the stable parison test.
• the stable parison is substantially free of imperfections such as holes or significantly thickened or thinned wall regions.
• stable parison test describes a test to determine whether a composition is blow-moldable.
• a composition passes the stable parison test if the composition can be extruded at 288 °C downwardly into a parison having a 7 mm wall thickness and a 25 mm outside diameter at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and the wall thickness throughout remains above 6 mm and below 8 mm for at least 30 seconds after the hanging length of the parison reaches 1 meter.
• “Amplify® GR216” is a maleic anhydride grafted elastomer and is commercially available from Dow Chemical.
• the formulation “PA66/DI” used in the examples of the present disclosure has an RV of 45, and a composition of 92:8 PA66:DI (wt/wt), with the “DI” part being about 40:60 D:I (wt/wt) or 50:50 D:I (molar).
• RV Relative viscosity
• AEG is an abbreviation for amine end groups present in the polyamide resin and is measured in moles per million grams (mpmg) or milliequivalents per kg (meq/kg). AEG is determined by titration of polymer solution in solvent such as methanol/phenol.
• ISO 527 Tensile strength (MPa) measurement and % elongation-at-break measurement method.
• Table 2 lists compositional ranges of several polyamide samples that are compounded using the general procedure detailed above.
• formulation “F”, as described in Table 2, is fed to a blow molding processing step for preparing blow-molded parts of various shapes. It is noted that formulation “F” is difficult to blow mold into articles due to its poor melt strength, especially in the absence of any reinforcement additive (GF, for example).
• GF reinforcement additive
• the formulation “B”, as described in Table 2, is fed to a blow molding processing step for preparing blow-molded parts of various shapes. Surprisingly, the formulation “B” displays great processability and superior melt strength during blow molding and in the absence of any reinforcement additives.
• Various blow-molded articles are obtained having the wall thicknesses in the 0.5-20 mm range and of aspect ratios (L/D) in the 0.5-75 range.
• An aspect ratio is defined as an arithmetic ratio of the overall linear length of a shaped article over its diametric distance.
• a shaped blow-molded article of 50 cm linear length (L) and 10 cm overall diameter (D) will have the aspect ratio of 5.
• the test material had 255 °C melt point temperature, 1.04 g/cc density, and 3.1 g/10 cc MFR value (290 °C/15 kg conditions).
• the test material is dried using -30 °C dew point air at >100 °C temperature in an industrial-size desiccant drying system.
• the molded part resembles a three-dimensional, hollow, duct-like piece having about 25 mm outer diameter x 90 mm developed length and about 2-2.5 mm wall thickness.
• the duct-like piece includes a combination of straight sections and several helical/curved sections for testing the mold quality at tight curves/bends.
• test material in suction blow molding is evaluated by observing the melt strength, swelling ratio, elasticity/toughness, outer/inner part appearance aspects, and material stability, as described below.
• melt Strength and Swellins Ratio The melt strength is determined by expulsion of a parison and time measurement until the parison hits the lower plate of the machine. The expulsion speed and die gap-opening are kept constant. During the dynamic expulsion, the parison is stretched under its own weight. The drop-time is then related to the parison strength. The test conditions are: 1.8 m drop height, 2% expulsion speed, 50% die gap. Three melt temperatures are used during the parison drop test (“PDT”).
• the measured drop times are: 27 sec (at 276 °C), 26 sec (at 285 °C), and 25 sec (at 295 °C).
• the 20 °C increase in the melt temperature only slightly affects the parison strength.
• the swelling ratio is determined by dividing the parison outer diameter by the die diameter. For all the above melt temperatures, the swelling ratio is 2.13 (17 mm parison diameter / 8 mm die diameter). The data indicates that the swelling ratio is not impacted by the 20 °C increase in the melt temperature.
• the regrind material is produced by regrinding once-molded parts obtained from the neat material.
• the grinding is done by rotating blades equipped with a 6-mm diameter calibrated grid.
• the regrind material is immediately dried at about 90 °C for 4 hours to minimize moisture pickup.
• An automatic blending device is used to prepare the 70:30 neat:regrind blend.
• the melt processing temperatures are: 275 °C (min) / 285 °C (optimum) / 290 °C (max) / 40-90 °C mold temperature.
• the blow-molded part resembles a hollow 3 -dimensional air-duct-like part having about 42 mm average diameter x 550 mm developed length, and approximately 380 grams of full weight in production.
• the swelling ratio is determined by dividing the parison (outer) diameter with the die diameter. Table 3b shows the swelling ratio results for the three materials that are tested. The use of regrinds slightly increases the swelling ratio.
• Table 3d summarizes the mechanical performance data for the molded material including the regrind content.
• Samples A, C, and D pass the stable parison test.
• the maximum difference in wall thickness is 14% of 7 mm, 13% of 7 mm, and 12% of 7 mm, respectively.
• Sample E passes the stable parison test.
• the maximum difference in wall thickness is 7.5% of 7 mm.
• Table 4 shows additional samples that are compounded according to the procedure of Example 1 and then subjected to the stable parison test.
• P indicates that the sample passes the stable parison test
• F indicates that the sample fails the stable parison test.
• Stable parison test maximum difference from extruded wall thickness indicates the maximum difference in wall thickness after 30 seconds after attaining the 1 m length, in terms of the percentage of the original wall thickness.
• Aspect 1 provides a blow-moldable composition comprising: a polyamide composition, a reacted composition that is a reaction product of the polyamide composition, or a combination thereof, the polyamide composition comprising
• Aspect 2 provides the blow-moldable composition of Aspect 1, wherein the reinforcing fiber is glass fiber.
• Aspect 3 provides the blow-moldable composition of any one of Aspects 1-2, wherein the polyamide-6,6 is from >30 wt% to ⁇ 70 wt% of the polyamide composition.
• Aspect 5 provides the blow-moldable composition of any one of Aspects 1-4, wherein the polyamide-6,6 has an AEG of >65 milliequivalents per kg (meq/kg) and ⁇ 130 meq/kg.
• Aspect 6 provides the blow-moldable composition of any one of Aspects 1-5, wherein the polyamide composition further comprises a PA66 copolymer.
• Aspect 7 provides the blow-moldable composition of Aspect 6, wherein the PA66 copolymer is from >10 wt% to ⁇ 50 wt% of the polyamide composition.
• Aspect 8 provides the blow-moldable composition of any one of Aspects 6-7, wherein the PA66 copolymer is from >25 wt% to ⁇ 35 wt% of the polyamide composition.
• Aspect 9 provides the blow-moldable composition of any one of Aspects 6-8, wherein the PA66 copolymer is nylon 66/6T, nylon 66/DI, nylon 66/D6, nylon 66/DT, nylon 66/610, nylon 66/612.
• Aspect 10 provides the blow-moldable composition of any one of Aspects 6-9, wherein the PA66 copolymer is PA66/DI.
• Aspect 11 provides the blow-moldable composition of any one of Aspects 6-10, wherein the PA66 copolymer is PA66/DI, and wherein the PA66 copolymer is from >25 wt% to ⁇ 35 wt% of the polyamide composition.
• Aspect 12 provides the blow-moldable composition of any one of Aspects 1-11, wherein the maleic anhydride-grafted polyolefin has a grafted maleic anhydride incorporation of >0.05 wt% to ⁇ 1.5 wt% based on a total weight of the maleic anhydride-grafted polyolefin.
• Aspect 13 provides the blow-moldable composition of any one of Aspects 1-12, wherein the polyamide composition further comprises a chain extender.
• Aspect 15 provides the blow-moldable composition of any one of Aspects 13-14, wherein the chain extender is >0.1 wt% to ⁇ 1 wt% of the polyamide composition.
• Aspect 16 provides the blow-moldable composition of any one of Aspects 13-15, wherein the chain extender comprises a dialcohol, a bis-epoxide, a polymer comprising epoxide functional groups, a polymer comprising anhydride functional groups, a bis-N-acyl biscaprolactam, a diphenyl carbonate, a bisoxazoline, an oxazolinone, a diisocyanate, an organic phosphite, a bis-ketenimine, a dianhydride, a carbodiimide, a polymer comprising carbodiimide functionality, or a combination thereof.
• the chain extender comprises a dialcohol, a bis-epoxide, a polymer comprising epoxide functional groups, a polymer comprising anhydride functional groups, a bis-N-acyl biscaprolactam, a diphenyl carbonate, a bisoxazoline, an oxazol
• Aspect 17 provides the blow-moldable composition of any one of Aspects 13-16, wherein the chain extender is a maleic anhydride-poly olefin copolymer, such as an alternating copolymer of maleic anhydride and ethylene.
• the chain extender is a maleic anhydride-poly olefin copolymer, such as an alternating copolymer of maleic anhydride and ethylene.
• Aspect 18 provides the blow-moldable composition of any one of Aspects 13-17, wherein the chain extender is a maleic anhydride-poly olefin copolymer, and wherein the chain extender is >0.1 wt% to ⁇ 1 wt% of the polyamide composition.
• Aspect 19 provides the blow-moldable composition of any one of Aspects 13-18, wherein the chain extender, or domains thereof, is/are uniformly distributed in the polyamide composition and/or the reacted product thereof.
• Aspect 20 provides the blow-moldable composition of any one of Aspects 1-19, wherein the polyamide composition further comprises a modified polyphenylene ether, an impact modifier, a flame retardant, a chain extender, a heat stabilizer, a colorant additive, a filler, a conductive fiber, another polyamide other than the polyamide-6,6, or a combination thereof.
• Aspect 21 provides the blow-moldable composition of any one of Aspects 1-20, wherein the blow-moldable composition comprises the polyamide composition.
• Aspect 22 provides the blow-moldable composition of any one of Aspects 1-21, wherein the blow-moldable composition comprises the reacted composition that is the reaction product of the polyamide composition.
• Aspect 23 provides the blow-moldable composition of any one of Aspects 1-22, wherein the blow-moldable composition comprises the polyamide composition and the reacted composition that is the reaction product of the polyamide composition.
• Aspect 24 provides the blow-moldable composition of any one of Aspects 1-23, wherein the polyamide-6,6 is from >40 wt% to ⁇ 50 wt% of the polyamide composition, and wherein the polyamide composition further comprises PA66/DI that is from >25 wt% to ⁇ 35 wt% of the polyamide composition.
• Aspect 25 provides the blow-moldable composition of any one of Aspects 1-24, further comprising from >0 to ⁇ 1 % by weight of nylon-6.
• Aspect 27 provides the blow-moldable composition of any one of Aspects 1-26, wherein the blow-moldable composition forms a parison that: remains substantially stable in an open split mold of a blow molding process for time >1 second and ⁇ 60 second.
• Aspect 28 provides the blow-moldable composition of Aspect 27, wherein the parison is blow-moldable at ratios of volume to surface area selected from:
• Aspect 29 provides the blow-moldable composition of any one of Aspects 1-28, wherein the blow-moldable composition is extrudable downwardly at a temperature of 260 °C to 310 °C into a parison having a wall thickness of Wi at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and a wall thickness of the parison throughout differs from Wi by less than [0156]
• Aspect 30 provides the blow-moldable composition of any one of Aspects 1-29, wherein the blow-moldable composition is extrudable downwardly at a temperature of 260 °C to 310 °C into a parison having a wall thickness of Wi at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and a wall thickness of the parison throughout differs from Wi by less than 15% of Wi for at least 30 seconds after the length of 1 meter is reached.
• Aspect 31 provides the blow-moldable composition of any one of Aspects 1-30, wherein the blow-moldable composition is extrudable downwardly at a temperature of 260 °C to 310 °C into a parison having a wall thickness of 7 mm and a 25 mm outside diameter at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and a wall thickness of the parison throughout remains above 6 mm and below 8 mm for at least 30 seconds after the length of 1 meter is reached.
• Aspect 34 provides the blow-moldable composition of any one of Aspects 1-33, wherein the maleic anhydride-grafted polyolefin, or domains thereof, is/are uniformly distributed in the polyamide composition and/or the reacted product thereof.
• Aspect 37 provides the blow-moldable composition of any one of Aspects 35-36, wherein the blow-molded composition that is reused in the blow-moldable composition is ground prior to incorporation into the polyamide composition of any one of Aspects 1-44.
• Aspect 38 provides the blow-moldable composition of any one of Aspects 35-37, wherein the blow-molded composition that is reused in the blow-moldable composition is formed to a particle size of 10 mm or less prior to incorporation into the polyamide composition of any one of Aspects 1-44.
• Aspect 39 provides the blow-moldable composition of any one of Aspects 35-38, wherein a parison formed from the blow-moldable composition has a swell ratio that is substantially the same as a swell ratio of a parison formed during formation of the blow-molded article that is reused in the blow-moldable composition.
• Aspect 42 provides a blow-moldable composition
• a blow-moldable composition comprising: a polyamide composition, a reacted composition that is a reaction product of the polyamide composition, or a combination thereof, the polyamide composition comprising >30 wt% to ⁇ 90 wt% polyamide-6,6, and from >0 wt% to ⁇ 10 wt% of a reinforcing fiber; wherein the blow-moldable composition is extrudable downwardly at a temperature of 260 °C to 310 °C into a parison having a wall thickness of Wi at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and a wall thickness of the parison throughout differs from Wi by less than 30% of Wi for at least 30 seconds after the length of 1 meter is reached.
• Aspect 43 provides the blow-moldable composition of Aspect 42 wherein the parison is blow-moldable at ratios of volume to surface area selected from:
• Aspect 44 provides a blow-moldable composition comprising a polyamide composition, a reacted composition that is a reaction product of the polyamide composition, or a combination thereof, the polyamide composition comprising
• PA66/DI that is from >25 wt% to ⁇ 35 wt% of the polyamide composition, and from >10 wt% to ⁇ 50 wt% of a maleic anhydride-grafted polyolefin, the maleic anhydride-grafted polyolefin having a grafted maleic anhydride incorporation of >0.05 to ⁇ 1.5 wt% based on total weight of the maleic anhydride-grafted polyolefin; wherein the blow-moldable composition is extrudable downwardly at a temperature of 260 °C to 310 °C into a parison having a wall thickness of Wi at a linear extrusion rate of 6-8 cm/sec to a length of 1 meter, and a wall thickness of the parison throughout differs from Wi by less than 30% of Wi for at least 30 seconds after the length of 1 meter is reached.
• Aspect 45 provides a blow molded article comprising the blow-moldable composition of any one of Aspects 1-44.
• Aspect 48 provides a blow molded article comprising: a polyamide composition, a reacted composition that is a reaction product of the polyamide composition, or a combination thereof, the polyamide composition comprising
• PA66/DI that is from >25 wt% to ⁇ 35 wt% of the polyamide composition, and from >10 wt% to ⁇ 50 wt% of a maleic anhydride-grafted polyolefin, the maleic anhydride-grafted polyolefin having a grafted maleic anhydride incorporation of >0.05 to ⁇ 1.5 wt% based on total weight of the maleic anhydride-grafted polyolefin.
• Aspect 49 provides a method of making the blow-moldable composition of any one of Aspects 1-44, the method comprising: combining the polyamide-6,6 and the maleic anhydride-grafted polyolefin to form the blow-moldable composition of any one of Aspects 1 -44.
• Aspect 50 provides the method of Aspect 49, wherein the method comprises combining the polyamide-6,6 and the maleic anhydride-grafted polyolefin prior to adding a chain extender thereto.
• Aspect 62 provides the method of any one of Aspects 60-61, wherein the incorporation into the first compounded polyamide melt comprises formation of a reaction product of the maleic anhydride-grafted polyolefin.
• Aspect 65 provides the method of any one of Aspects 60-64, wherein the introducing of the chain extender to the first compounded polyamide melt in the second compounder extruder zone comprises introducing the chain extender to the first compounded polyamide melt after at least 60 wt% of the maleic anhydride-grafted polyolefin has incorporated into the polyamide-6,6.
• Aspect 67 provides the method of any one of Aspects 60-66, wherein the introducing of the chain extender to the first compounded polyamide melt in the second compounder extruder zone comprises introducing the chain extender to the first compounded polyamide melt after at least 80 wt% of the maleic anhydride-grafted polyolefin has incorporated into the polyamide-6,6.
• Aspect 68 provides the method of any one of Aspects 60-67, wherein the introducing of the chain extender to the first compounded polyamide melt in the second compounder extruder zone comprises introducing the chain extender to the first compounded polyamide melt after at least 90 wt% of the maleic anhydride-grafted polyolefin has incorporated into the polyamide-6,6.
• Aspect 69 provides the method of any one of Aspects 60-68, wherein the introducing of the chain extender to the first compounded polyamide melt in the second compounder extruder zone comprises introducing the chain extender to the first compounded polyamide melt after about 100 wt% of the maleic anhydride-grafted polyolefin has incorporated into the polyamide-6,6.

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